Diazoamino compounds



Patented 'July- 26, 1938 UNITED STATES PATENT OFFICE 2,124,594 I DIAZOAMINO COMPOUNDS Albert, Schmelzer, Cologne/Rhineland, Germany, assignor to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No-Drawing. Application July 20, 1937, Serial No.

154,633. In Germany July 25, 1936 5 Claims.

ing groups in the radical, attached to the amino nitrogen and are free from such groups in the radical attached to the -.N =N--, as they are soluble in water and yield on. spitting a? diazo compound of an aromatic radical which is free 2 from groups inducing solubility in water. Up to the present only such diazoamino compounds havebeenemployed in practice as have the acid groups neutralized by means of alkali metals.

I have nowfound that'volatile basesalts of such diazoamino compounds exert new andunexpected properties which make them particularly suitable for the purpose indicated'above; These volatile base salts are characterized by their being known alkali metal salts. In consequence thereof, in most cases a mere blowing in of water vapour or steaming of these products is sufficient to efiect the splitting up into'the diazo compound 5 and the stabilizer. This is most probably due to the fact that the volatile bases evaporate while hot thus imparting to the remaining preparation an acidity which is sufficient for effecting the spitting up of the same. In consequence thereof, the expensive and troublesome treatment with acid vapours can be dispensed with or "at least the quantity of acid vapours can be mate rially decreased. 5 V

My new diazoamino compounds can bepre- 45. pared generally by dissolving the stabilizer in' water, adding thereto an excess of ammonium carbonate and then the diazo compound; when working in this manner, the ammonium salt of the diazo amino compound precipitates in most cases. Salts of volatile amines are prepared by dissolving the stabilizer in an aqueous solution of ydrogen halide; also in these cases the. volatile.

base salt precipitates in most cases. "If it is ,too

much more easily split up than the hitherto" easily soluble in water it can be isolated by evaporation in the vacuo or by salting out with, for instance, ammonium chloride. Such amines are preferred as have a boiling point between about 30 C. and about C. r 5;.

The following examples illustrate the invention without, however, restricting it thereto the parts being by weight:-- 1

Example 1' V 10 42.5 parts of 4-chloro-2-toluidine are sus- I pended in 250 parts of water and parts of hydrochloric acid and diazotized at a temperature of 10-12 C. witha solution of 20.5 parts of sodium 15;.

nitrite in 50 parts of water. The diazo solution is filtered and at 0 to +5 C. quickly added to a solution of 80 parts of 4-sulfo-2-aminobenzoic acid in 700 parts ofpyridine, which is diluted with 300 parts of water, while thoroughly stirring the mixture. After 4-5 hours stirring no diazo compound can be traced. Then the mixture is diluted with about 1000 parts of water and salted out with about 500 parts of ammonium chloride.

The pyridine salt of the diazo amino compound 25 precipitates in yellow crystals. .The product filtered with suction is dried in the open air. This diazoamino compound has'probably the following formula:

Example 2 amps-its of 4-chloro-2-toluidine are diazotized' as described in Example 1. At a temperature of about -4 C. the filtered diazo solution is added quickly to a solution preparedfrom80' parts of 4-sulfo-2-amino-benzoic acid, parts of ammonium carbonate and 800 parts of water while stirring thoroughly. Coupling occurs with the evolution of carbon dioxide. A diazoamino com- 55f ing formula is obtained:

pound probably of the following formula precipitates in yellow crystals;

CH3 S OaNH4 l C 0 ONE! After about 3-4 hours stirring no more diazo compound is traceable. The mixture is filtered with suction and thoroughly dried.

Example 3 If '76 parts of 5-sulfo-3-aminobenzoic acid are used instead of the 4sulfo2 ami nobenzoic acid a diazoamino compound probably of j the follow- As it does not precipitate from the solution, it is isolated by salting out with about'350 parts of sodium chloride; it shows a yellow coloration.

Ezrample 4 When using 115 'partsof isobutyl-5-sulfo-2- amino-benzoic acid under the conditions mentioned in'Example 2, a diazoamino compound probably of the following'formulais obtained:

The product crystallizes in yellow crystals. It is worked up as described in Example 2.

. n Example 5 V a 42.5 parts of l-chloro-2 toluidine are diazotized according to theinstructions given in ExampleZ; V the solution is then made slightly acid to Congo red by addition of a solution of 25 parts of am- The working up is performed as described above. If the aminoterephthalic acid of the above example is substituted by the aniline-2.5-disulfonic acid, the corresponding diazoamino compound also precipitating from the reaction mixturein yellow crystals is obtained.

' Example 6 48.6 parts of 2,5}dichloraniline are suspended in 'a solution of 130 parts of hydrochloric acid in 230 following formula:

parts of water and diazotized at a temperature of 10-15 C. with 20.5 parts of sodium nitrite, dissolved in 50 parts of water while stirring thoroughly. The diazo solution is neutralized and filtered if necessary; about 25 parts ofamrnonium carbonate dissolved in parts of water are added thereto. While stirring thoroughly at about -4 C. to 0 C. this solution is added drop by drop to a solutionvof 80 parts of 4-sulfo-2- aminobenzoic acid in 800 parts of water having admixed. therewith. parts of ammonium carbonate.

A yellow colored diazoamino compound probably of the following formula:

precipitates. As it is'ratherdiflicultly soluble in water, it is washed and dried thoroughly after having been filtered with suction. 7

Example 7 48.6 parts of 2,5-dichloraniline are diazotized as described in Example'6 and added 'drop by drop at 0 to +10 C. to a solution of 80 partsof v4-sulfo-2-aminobenzoic acid in 840 parts 'of a sodium carbonate solution of 16.5% strength while stirring thoroughly. When diazo compound can no longer be traced, it is salted out with. about 200 parts of ammonium-chloride, stirring being continued-for. 2 hours, and then filtered with suction. The diazoamino compound part in the r thus isolated is present at least in form'of its ammonium salt.

Example 8 According to the directions given in Example 6 2,5-dichl0raniline is diazotized whereupon the diazo solution is neutralized. The 4-su1fo-2- aminobenzoic acidis replaced under the same conditions by 72 parts of 5-sulfo-2-aminobenzoic acid. In this case the diazoamino compound is salted out by means of 350 parts of sodium chlo-' ride and carefully dried after having been rinse with a 75% sodium chloride solution. g r

7 Example 9 46.4 p'arts of 5-.nitio-2-toluidine areadded 1:0"

asolution' consisting of115 parts of hydrochloric acid and 150 parts of water. The amine is then diazotizepd at 10-12" C. by stirring with 20.5 parts of an aqueous sodium nitrite solution. After neutralizing by means of parts of a 20%.

ammonium carbonate solution the reaction product is filtered, whereupon the diazo solution is caused to react, with a. solution of 80 parts of "the ammonium salt of l-'sulfo-Z-aminobenzoic acid The .diazoamino as set forth in Example '6. compound which probably corresponds. to the is salted outiby means of'lSOO parts of am-.

monium chloride; it forms deeply yellow crystals whichare filtered with suction and carefully dried.

Example On replacing the 4-sulfo-2-aminoben'zoicacid by 5-sulfo-2-aminobenzoic acid there is obtained according to the directions given in Example 9 a diazoamino compound probably of the following formula:

v SOaNHl C OONH which may also be salted out from the reaction mixture.

Example 11 is filtered with suction, rinsed with a 75% saturated sodium chloride solution and carefully dried.

Example 12 On replacing the diethylamine employed in Example 10 by 69 parts of a 95% triethylamine a diazoamino compound probably of the following formula is obtained: I

C2115 0 Ha S O s'-N l oz a -N=NNHC mm C 2115 Cl The product separating out is worked up as described in Example 10.

Example 13 111.1 parts of an 80% paste of 2-amino-5- benzoylamino-hydroquinonediethylether are finely suspended in 90 parts of water and 140 parts of raw hydrochloric acid and then diazotized at a temperature of -20 C. by means of a solution of 26 parts of sodium nitrite in 65 parts of water. The solution is filtered and at 15 C. added while stirring to a solution of 41.1 parts of sarcosine chlorohydrate and 164 parts of ammonium carbonate in 500 parts of water. When no diazo compound can be traced any more, the precipitated cliazoamino compound which probably has the following constitution:

(llCzHs is sucked off and dried. It represents a weakly yellowish powder. 1 Example 14' 59.4 parts of 4-chloro-2-anisidine chlorohydrate are diazotized as described in Example 1.

The filtered solution is added into a solution of 80' parts of 4-sulfo-2-amino-benzoic acid and 140 parts of ammonium carbonate in 500 parts of water, below 0 and while stirring. The diazoamino compound which probably has the follow:

ing constitution:

0 on, $0. m.

, COONHI a v p precipitates; it is isolated in the usual manner.

Example 15 The diazo compound of Example 13 is added While stirring at a temperature of 15 C. to a solution of 80 parts of 4-sulfo-2.-aminobenzoic acid'and130 parts of ammonium carbonate in 500 parts of water. The reaction being finished the precipitating yellowish ammonium salt of the diazoamino compound is sucked off and dried.

Example 16' When using a mixture of 65.7 parts of 4-toluidine-Z-sulfonic acid under the conditions described in Example 2, a diazoamino compound of the following probable constitution is obtained:

The product precipitates in weakly yellowish crystals.

Example 17 When using a mixture of 44.5 parts of methyltaurine under the conditions of ExamplelB the ammonium salt of the diazoamino compound of methyltaurine and 2-amino-5-benzoyl-aminohydroquinone diethylether is obtained 7 in form of a greenish-grey powder.

Example 18 When using 53 parts of methylamino succinic acid under the conditions of Example 13 the diazoamino compound of the following probable formula is obtained:

CH: CHr-C OONH4 NH O O CaHa 0 0211s The product shows a yellow coloration.

v c a l act with sarcosine chlorohydrate and ammonium i Example 19,

136.2 parts of a 60% past of2 amino-5-ben zoylamino-hydroquinonedimethyl ether are diazotized and caused to react with 43.5 parts of iminodiacetic acid dissolved in water under the conditions described in Example 13; the following diazoamino compound is obtained:

carbonate under the conditions described in Example 13. The following diazoamino compound is obtained:

(i)CHa CH3, 7 Example 21 V G 0 Cells 'When using 78.4 parts pf betag-m ethylamidotetrahydro naphthalene monosulfonic acid. under the conditions of Example 13 the, following diazoamino 1 compound is obtained;

ZQO HQ T U c This product shows a brown coloration.

cm c o o NHl Example 2 2,

r ;When using 69.4; parts I of tetrahydroguinoline monosulfonic acid'under theconditions of Example 13, the following diazoamino compound is obtained; V V V V 7 002115 l CH:-CH2

This compound precipitates in form of 'an orange colored powder.

Example 23 a H 37.2 parts of pyrolidine-alpha-carboxylic' acid" are used for the preparation'of the diazoamino compound under the conditions of Example 13. The following product is obtained:-

OCzHs r M r i l. h, p H ,3.

N=NIN-- i on olr NH I 25 1 r a 000N114, Q 0 02m 7. 3 c i .451 i' This diazoamino compound precipitates. in

weakly greyish-colored crystals.

I claim: 1. Volatile'base salts of diazoamino compounds containing acid salt forming groups in the radical attached to the amino nitrogen.

2. The products as claimed in claim 1 wherein the volatile bases are alkyl amines of a boiling point between about 30C. and about 80 C.

3. The products as claimed in claim 1 wherein diethylamihe is employed as volatile base.

4. The products as claimed in claim 1 wherein 40 ammonia is employed as volatile base. I 1 J 5 5. The products as claimed in claim 1. wherein the Volatile base is an alkyl'amine.

AIJBERT SCHMELZER. 

